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Patented'Nov. 26, 1946
’
UNITED ' STATE s.‘
2,411,671
PATENT. OFFICE
2.411.611
-
tum-mar, on. ooMPosmoN RESISTANT
.
'ro meme; 1
'
-
-
_
Herschel G. Smith, vwaningmid,‘ and Troy L.
Cantrell, Lansdowne, Pa... assignors to Gulf Oil
Pennsylvania
Corporation, Pittsburgh, Pa., ajcorporation of
No Drawing. Application‘ March 12, 1945, .
Serial No. 582,402
7 Claims.
(Cl. 252-325) '
1
.
This invention relates to improved mineral oil
compositions resistant to foaming.
2
is objectionable. For example, as an airplane
climbs to high altitudes, the temperature and
_
In lubricating machinery and other devices
with oils, in handling oils as by pumping, in hang
pressure of the :oil in the sump and oil lines may
be decreased, conditions which promote foamin
dling oil under reduced pressures and in trans
mitting power with an oil medium, conditions are
- tendencies which are highly undesirable.
Another field of use is in oils used in so-called
often such that the oil is subjected to violent
?uid drives or in hydraulic drives or systems.
With these types of oils which are often of vis
agitation in the presence of air or other gases;
conditions such as to produce foam or froth. In
cosity as low as SAE 10 grade, agitation may 1 ‘
most cases foaming or frothing is quite objection 10 produce considerable foam, even though the foam
able. For example, in crankcases of internal
subsides ‘very quickly on ceasing agitation. Our
combustion engines or in the lubrication of gears
new agents are also useful in cutting oils and
the foaming produced by the churning of the
quenching oils and indeed in any oil or oily com
gears gives rise to excessive leakage, improper
position whether used as a lubricant or not.
lubrication, and loss of lubricant past retainer 15
rings, etc.
Gears such as those used in transmis- -
Several methods for preventing the foaming
of mineral oils have been proposed heretofore.
sion and differential gear assemblies often oper
The procedure has been to prepare a comparar
ate at very high speeds, as well as under high
tively unstable product, emulsions which sepa
tooth pressures; therefore they require a very
rate free oil which acts somewhat as a foam sup
good lubricant to prevent or retard excessive wear 20 pressor. Another method is to add aluminum
due to surface~to~surface contact.
stearate to the oil; these methods have objection
able characteristics.
The lubricants employed usually are viscous
oils, often containing a so-called extreme pres
Among the objects of our i ivention is provision
sure agent to assist in maintaining an oil ?lm
of a mineral oil composition resistant to foaming,
between the teeth; sulfurized sperm oil is an 25 and a method of suppressing the foaming of min
especially good pressure carrying agent. If the
eral oils and oil compositions and other inhibited
lubricant contains air dispersed through it, it
lacks proper ?lm forming properties. In reduc
tion gears, particularly herringbone gears, oil
lubricating compositions which are characterized
by a decreased tendency to foam or froth under
severe conditions.
30
We have discovered a class of compounds
aerofoam is undesirable as it tends to produce pit
ting or corrosion at the point of maximum pres
sure. Moreover, foaming oil is usually much less '
effective in conducting heat away from the work
ing zone. These dii?culties are often aggravated
which are effective as inhibitors in lubricating oil
compositions in reducing the foaming tendency
of mineral oils, salts of an alkyl alkylene diphos
phate having the following general formula:
by the fact that some extreme pressure agents 35
present in the oil actually increase the foaming
characteristics of the composition.
Foaming is also objectionable in other situa
tions; for example, in compounding oils with ex
121
treme pressure agents and other additives, an 40
operation involving thorough agitation. Nearly
all petroleum oils foam to some extent under vio
lent agitation. The more viscous oil, the greater
the amount of foam, and the longer it persists
after agitation is stopped.
In pumping‘ oils with rotary gears, displace
ment, or other type pumps, foam or gas pockets
often interfere with the pumping of the oil, caus
ing a reduction in the stream of oil flow. This
condition may be caused by either the vacuum
on the intake or by the entrainment of gas due to
‘wherein R represents an alkyl group containing
1 to ‘18 carbon atoms, Y is a substituent of the
class consisting of monovalent metals and alkyl
groups, X represents a substituent of the class
45 consisting of metals and an organic ammonium
group derived from the class consisting of hetero
cyclie nitrogen bases and dialkylaryl amines, m
is a number corresponding to the valence of X,
and 'n is from 2 to 6. >
The monovalent metal represented in one em
bodiment of the above formula by Y may be any
violent agitation. In placing oil under vacuum,
element selected from group I of Mendelyeev’s
it sometimes is found that the. foaming charac
Periodic Table-of Elements. However, the met
teristic of the oil is such as tov cause loss of oil
als preferably used are sodium and potassium.
entrained in the gas removed. This loss of oil 55 Y may also represent an alkyl group containing
g
2,411,071
3
4
from 1 to 18 carbon atoms in the above general
formula for an alkyl glycol phosphate salt.
x may be a cyclic nitrogen base salt which
has as a nucleus alkyl substituted cyclic amines
n n a 11
no-t-é-é-la-on
1i 1!: 1i i
is the simplest one of these compounds. it being
a straight chain compound.
. having one or more rings, such as aniline, di
methylaniline, pyridine. nicotine, furazan and
the like. The alhvl groups attached to the nitro
gen of the cyclic nitrogen base salt may be hy
drogcn or other alkyl groups of any reasonable
length or configuration, but the longer chains‘
give increased solubility of the compound in oil.
Furthermore. x may represent an alkyl group
containing from 1 to 18 carbon atoms, providing
Y is a monovalent metal.
As to the “dihydric alcohol or glycols,” the
generic formula given is as follows:
The other "butylene glycols" ' are branched
chain compounds. For instance. izs-butylene
glycol has the following formula:
H B H
110-13-5-13-08
i1 1!; ts.
That is, it is a methyl substituted derivative of
betapropylene glycol wherein the methyl group is
. substituted for one of the hydrogens thereof.
The other branched chain "butylene glycols’I are
methyl derivatives of ethylene glycol. For in
That is, the glycols contain two hydroxyl groups
stance, "2:3-methyl-butane-2:3-dio ” or “pina
joined together by a "bivalent alkylene" radical. 20 cone" has the following formula:
CaHsdOI-I) :
Thus, the structural formula may be written as
HsC CH:
follows:
E0- -o-on
Ha
\
Es
wherein n represents the number of carbon atoms
in the alkylene radical; 1: usually being 2 to 6, 25 It is also known as "tetramethyl-ethylene gly
as shown in the speci?c examples of the known
col"; the four hydrogens of ethylene glycol being
glycol compounds.
'
Some of the speci?c glycol compounds useful
in our invention may be described as follows:
Errrrun Garcon
substituted with methyl
As a class, such methyl substituted ethylene
glylilz‘ols may be represented by the following for
m
'
35
n n
Obviously,
30 pylene glycols mentioned ante.
There is only one ethylene glycol (dihydroxy
ethane). This compound has the following for
mula:
groups.
other methyl substituted ethylene glycols are pos
sible in addition to the pinaeone and alpha-pro
HO-Zt-Ji-OB
:
all.“
L t
wherein Z represents hydrogen or a methyl group.
It is typical of the glycols used in making the
That is, the above formula also includes ethyl
improvement agents of the present invention. 40 ene glycol (the parent substance) when all the
2's are hydrogen. On the other hand. when all
Psorm Garcons
the 2's are methyl groups, the compound is then
There are two propylene glycols, namely,
pinacone. the highest member of this subclass:
alpha-propylene glycol and beta-propylene gly
the total number of carbons in this compound
col; they being the "two" isomeric forms of this ' being 6.
compound. The alpha-propylene glycol is "pro
In fact. the speci?c examples mentioned on
pane-1:2-diol" and has the following formula:
these pages contain six or less carbon atoms.
H H
For instance, various amylene and hexyleneglycols are also known. However. while the two
subgeneric formulas given ante cover the higher
Hs
homologues of ethylene glycol, including the
That is, it is a methyl substituted ethylene glycol
methyl substituted derivatives thereof, and the
wherein one of the hydrogens of ethylene glycol
higher straight chain compounds. respectively.
has been replaced with a methyl group.
neither of them include 1:3-butylene glycol
On the other hand, beta-propylene glycol is
which is a methyl substituted derivative of beta
"propane-1:3-diol" and has the following for.‘
propylene glycol. Thus, we must rely on the
broad generic formulae for glycol to cover this
mula:
compound in making our glycol-phosphate anti
foam agents.
60
The generic formula for the ?lycols in this
invention is represented by the following for
mula:
That is, it contains a straight chain alnlene
HO-(CsHM-OH
group connecting the two hydroxyl groups there
of.
wherein n is a number from 2 to 6. The above
In other words. there are two types of higher (35 generic class includes two important major sub
homologues of ethylene glycol; namely, the
classes. namely, the straight chain compounds
straight chain glycols and the branched chain
and the branched chain compounds. The ad
glycols. Thus, the butylene glycols and other
vantageous straight chain compounds are the
80-43-42-011
will...
i.
higher alkylene glycols can be divided into two ,
subclasses on this basis.
I
70 subclass A as follows:
Subclass A (straight chain compounds)
BUTYI-lil'l Garcons
0f the several butylene glycols, the “-butylene
glycol" or "butane-1:4-diol" having the follow
in! formula
n
H
no-c-(crn).-(|:-on
75
i
2,411,071
wherein n is 2 to
6. Typical species
,
of this class are as follows:
illustrative
'
.
.
Ethylene glycol HO-CHPCHPOH _____________ __ ethane diol
Propylene glycol HO—CHr-(CH1)—CH,—0H _ propane-ltiivdiol
Butyleue glycol HO—CHI—(CHIlr—'CH¢-—OH.__ butane—l:4-d1ol
Amylene glycol H0—CH1—-(CH:)r-CH¢'— H
The above straight chain .glycols are useful in
mahng the improved agents of the present in
vention. Likewise, the isomeric compounds 10
which contain a branched chain alkylene group
are also; useful for this purpose, particularly
centrated solution in oil; the concentrate con
those of the subclass B post.
tained approximately equal parts by weight of
The above compound‘ was prepared as a con
.
oil and anti-foam agent. The detailed procedure
Subclass B (methyl-substituted ethylene glycols)
*
I
'f a
employed was as follows:
no~e~<lz--on
,
.1
'
62 lb. of ethylene glycol and 390 lb. of octyl
alcohol (Z-ethyl hexanol) were added to a suit
able vessel and the temperature brought to 100°
F. To this mixture 306 lb. of phosphorus oxy
R
t t
wherein R represents a substituent of the class 20 chloride (POCla) were added over a period of two
consisting of hydrogen or alkyl groups. The fol
hours at such a rate to allow the hydrochloric
lowing'compounds are illustrative of this advan
acid evolved to escape from the reaction mixture
tageous subclass of glycols:
without ?ooding the re?ux condenser. The re
action mixture was then slowly heated at such
Ethylene glycol HO—-CH2—CHz-—0H_._ Uglssvyigsltituted ethylene 25 a rate as to raise the temperature 25° F. per hour
,
I
H
until it reached 300“ F. At this point the re
action mixture was cooled at 200° F., and a so
lution of potassium bicarbonate was added to
H
-ePropylene glycol H0— ~('J——0H __________ .. Propane-lzZ-diol
Ha
1
III
H
I
H
hydrolyze the residual chlorine and to neutralize
30
_
product obtained from this reaction was then dis
solved in an equal weight of mineral Coastal oil
having a viscosity of 100 seconds at 100° F. SUV,
then passed through a ?lter to remove the salt
-Butylene'glycol HO—-('}—(‘)—OH ............ _. Butane-2:3-diol
4
‘Ha
HI
H3O CH3
Tetramethyl-ethyiene HO—C-~(I‘J-—OH____ 2:3-dimethyl-butane
I
Ha
35
2:3-diol (pinacone) .
CH3
the acidity developed during the hydrolysis. The
and other impurities developed in the reaction.
The recovered solution comprised mineral oil,
potassium tri-octyl ethylene diphosphate.
,
An aviation and automotive lubricant was in
The above compounds are representative of a
methyl-substituted ethylene glycol wherein one
hibited with 0.05 per cent by weight of potas
Further, other methyl-substituted alkylene gly
according to the above procedure. The addition
of the aerofoam inhibitor to the following oil did
or more hydrogen is replaced with a methyl group. 40 sium tri-octyl ethylene di-phosphate, prepared
cols are also useful for the present purposes, as
not change the inspection properties very much,
shown in subclass C below.
Subclass C (methyl-substituted propylene glycols) 45
.
_
H
H
as is noted from the following table:
H
Base oil
1:3-butylene glycol HO- —-C‘J—!IJ—OH
I -
'
H:
-
di-phosphate
III
H
50
H
H2O
I The‘ above com-pounds are illustrative of the meth
yl-substitut‘edpropylene glycols and those con
useful'in' making the improvement agents of the
535
610
0
+5
_
Color, NPA .......... ..
_
5. 5
Carbon residue, percen ._
.
0. 54
0.46
Neutralization No ...... _.
_
0.05
0. 08
described
Composition
cedures have been found to be advantageous.
Certain of these advantageous procedures are il
lustrated by the‘following typical detailed meth
5. 5
ni‘it‘i‘ie‘t ‘3217
-
con a
g
invention._
Exmrr: I
octyl ethylene
di~phosphate
Temperature, ° F ______________ ._
80
78
Volume
of
ell audfforilm, eicf.cam
_____ . _
.
vo ume o 01 an
785
519
Ratio of -mm-. ..
1. 570
_ 1. 038
Nature of foam ................... ..
Coarse
Fine
After 1 hour standing:
Temperature, ° F ___________ _ _>_.. .
The ' potassium trioctyl-ethylene diphosphate
Volume
of
ell andffoalm, 30f.cam
_____ __
.
vo ume o 0! an
Rm’ 0‘ magma-~-
prepared according to the procedure described,
more fully in detail hereinbelow had the following
Nature of foam __________________ ._
75
.
strgillght of potassium tri‘3
At end of stirring:
*ods and‘are not intended to limit the scope of the
' formula:
535
610
Pour, ° F ___________ __
,
compounds
above. may be prepared in various ways, but in pre
_ paring anti-foam agents of this type, certain pro—'
.
26. 3
l, 841
118
However, the foaming tendency of the oil was
reduced greatly as shown by the following tests:
Gulf No. I foam test
taining'two or more methyl groups substituted
for the hydrogensof the propylene radical are also
.
26. 3
l, 845
119.9
210° F.
Flash, 00, ° F.
Fire, 00, °
1'1
The . glycol-phosphate
Gravity, ° API _____________________ _.
Viscosity, SUV:
100° F..-
-isobutylene glycol H0-o-<]J— ~03
present invention.,
Inhibited with
0.05% by weight
of potassium
tri-octyl ethylene
79
557
1‘ 114.,
Coarse
78
500
1- 000
None
8
7
the inhibited oil were not changed by the addi
Exams II
The percentage of inhibitor of Example I was
increased from ‘0.05 per cent by weight on the
tionotthisminoramountoioilaeroioamin
hibitor.
.
The following ioam test results show the dies
oil of potassium tri-octyl ethylene di-phosphate
to 0.10 per cent by weight on the oil. The oil 5 tivenees or our oil aeroioam inhibitor:
aerotoam evaluation data or the blank oil and
Gulf No. 1 loans test
the improved oil were as iollows:
Improved oil
Gull No. I {cum test
10
oompmuhn
Improved oil
‘
tri-ociyi ethylene
Btralifht cogmneiilglhg'uim
Mpumm
w
o
.
c
gotassium
At end of stirring:
di-phosphate
_______________ n
so
80
Volume oi oil andiiolalmhgc ...... ..
785
600
volume 0 o
loam
W9'mr~-
“7°
1~°°°
Nature ol ham .................. _.
Coarse
None
After i bournandin :
Volume‘ oroil'andgb‘?rill'géIIllI
volume 0 0 an roam
“WW-~‘
Nature of loam ................. ..
Temperature, 9 F _______________ ._
80
70
Volume 0!vo(‘iiiume
end'IoIalm.
(30m...
o 0 an
785
610'
M01 .._
1.670
1.088
Nature 0! loam .................. _.
Ratiooi “um on.
Coarse
Fine
AfterTemperature,
1 hour standing:
'
............... ..
79
.
20
Volume of
(‘all endfioelm, gel.oath
..... _ .
v0 nine 0 0 an
1s
557
.
000
n
79
Ratio Dim. __
1.114
LM
551
500
Nature oi loam .................. ..
Coarse
None
1-1“
1~°°°
Coarse
None
Exams IV
25
Burns: in
The following was the method employed in the
preparation or a dimethylaniline tri-octyl ethyl
ene di-phosphate anti-roam agent having the i0]
lowing formula:
diphospbate
_
tri-oetyl ethylene
At and oi stirring: .
y we
Btraioi t imw'iml
2%
methy'aniiine
C'H
The preparation of potassium dimethylaniline
di-octyl ethylene diphosphate was as follows:
To a suitable vessel 82 lbs. ethylene glycol and
260 lbs. octyl alcohol were added and brought to a
temperature of 100° 1"., and 308 lbs. oi phospho
30 rous oxychloride were added to this mixture at
To a suitable vessel 340 lbs. of well re?ned min
eral oil falling into the SAE 30 lubricating oil
classi?cation were added, and to the oil were 60
the rate or 25 per cent per hour; and the tem
perature was maintained below 160° F. After the
addition of the phosphorous oxychloride, the
temperature or the reaction mixture was gradu
ally increased to 300° 1". over a period of eight
hours. At this point live steam was admitted to
the reaction mixture to hydrobze the residual
chlorine contained in the phosphorous. Then
the temperature was allowed to drop to 212' 1''.
After hydrolysis, the product was partially neu
tralized with 56 lbs. of potassium hydroxide con
tained in a water solution (131 lbs. water). The
partially neutralized material was then heated to
240° I". to tree the reaction mixture from water;
the temperature or the reaction mixture then
dropped to 18° F., and 120 lbs. dimethylaniline
were added to complete the reaction. The mix
ture was then pumped out through ?lter-aid ?lter
to remove impurities resulting from the reaction
of the recovered reaction mixture which was
added 142 lbs( oi phosphorous pentoxide (PzOs);
ready then for use.
o! the oxide in the oil. Into another vessel 62 lbs. ‘
To the oil described in Example I was added
15 per cent by volume of a diluted suliurized
sperm oil. This superior extreme pressure lubri
cant was admixed with 0.05 per cent, by weight
35
40
40
andthemixturewaswellstirredtosecureaslurry
of ethylene glycol and 390 lbs. of octyl alcohol
were added. The oil suspension oi’ phosphorous
pentoxide was then slowly added at the rate or
50 per cent per hour to the alcohol solution, so
as to secure a smooth reaction oi the phospho
I
potassium dimethylaniiine di-octyl ethylene di
phosphate. The properties of the two oils were
as in?ows:
rous pentoxide with the alcohol-glycol mixture.
The temperature was held between 140° and 160' 60
_
then raised to 200°‘! and maintained at this
temperature while stirring for two hours. in order
to complete the reaction. This mixture was then
cooled to 150° I". and 122 lbs. dimethylaniline were
added over a period oi’ one hour and the temper
ature was maintained between 160° and 180° 1'‘.
The material was then passed through a ?lter to
clarify the reaction mixture.
volume 0!
MW
‘pm °"
Gravity, " API ..................... __
Viscosity SUV:
10ml‘ .... -
0° 1'‘...
a
'
dimetbylaniline tri-octyl ethylene diphosphate
preparedaccording to the procedure described
hereinabove in this example. The properties or 76
pouumm
9
7
dipgosphaie
20. 8
25. 7
1,341
rm
106. 0
400
550
+15
Tothehighlyre?nedviscousoildescribedin
Example I was added 0.05 per cent by weight of
Improved oil
23,121’;
15% by containing?“
by weig toi
during addition oi the oil suspension of the phos
phorous pentoxide. This reaction mixture was
it‘. 5
405
540
+16
5. 5
0. 52
5. 6
0. 48
.
(l 08
0. 02
Buliur, percent ...................... ..
l. 32
l. I)
Neutralization
o .... ._
The improved oil containing the 0.05 per cent ‘
2,411,071
by weight of potassium dimethylaniline di-octyl
' FOAM 'rnsr, GULF NO. 3
ethylene diphosphate was evaluated with Gulf
No. 1 foam test and the data were as follows:
Gulf No. 1 foam test
At end of 10 min. bubbling:
Volume of oil, co ________________ __
460
_
Rétio 0‘ volume of oil and foam
2 00
.1.
341
volume of original oil "‘
. 1.05
. Improved oil
-
.
2352111‘
00mposition
um
tors are effective in many types of'oils, bothun
5pem on dioctyll
ethylene H 0 compounded and compounded. Foaming'of oils
dip osphate
depends more on the type of oil, the type of~proc
essing which‘it has been through, and the inhibi
ture, ° F _______________ __
79
79
709
550
__..
1. 418
1.100
Nature oi’ loam;~ _______________ ..
Coarse
Fine
After‘l hour standing: \
'
Temperature, ° F _______________ -_
79
79
, 576
500 '
Volume of
oil andfloriilm, gain?" ,
v0 ume o 0 an 0am
Ratio 0'
As is shown in the above data our foam inhibi
by V1235 t of
g’gllggige‘g dinliji’aJthylaniline
At end oi’ stirring:
Tom
oontainin 0.05%
15% ‘>5
Volume of
(1)11 andtioiialm, so?0am
_____ ..
vo ume o 0 an
Ratio of WWI-CF ..._
1. 152
1. (XX)
Nature of foam .................. . i
Coarse
None
tors placed therein than on' the actual viscosity
of the oil at various temperatures.
in» various ‘types of oils havingother. pressure
carrying and antioxidant agents _‘therein. More- '
over, the foam inhibitors of this invention are
effective at various temperatures normally jen-‘v
20 countered in engine operation or other condi
tions to which the oil might be‘subjected, as shown
by the foam tests described more fully herein
below.
Gulf No. 2 foam vtest
C m
ition
0 pos '
Improved oil
Oil- 0on
-
containing 0.057
£23535,
bypovtgeight
of 0
ssium
To evaluate the foaming tendency of petroleum
oils and compositions a test was’ devised. which.
affords an exceptionally accurate indication of '
the comparative foaming tendencies. ' A sample -
‘7011?: 0: dimethylaniline
su- m “h (lioct lethylene
sperm‘)
dip osphate
At end of stirring:
Temperature, ° F ............... ..
79
79
Volume of
11:11 andtioiiilm, 3c; ..... _ _
vo ume o 0 an oam
950
575
Ratio 0’ volume of original oil T‘ '
1‘ 90
1: 15
Nature of foam __________________ _.
Coarse
vFine
of oil is subjected to very drastic foaming‘ condi-_
tions under a standardized procedure _which
30 makes it possible to determine quantitatively the
tendency of the oil to, foam and'the _stabilityor
permanency of the foam produced.
Temperature, ° F ............... __
75
78
Volume of
oil dtioiiilm, clef ..... ..
v0 ume 0 0 an 0am
650
500
Ratio 01W ___.
l. 30
1. 00
Nature of foam __________________ ..
Coarse
None
In general,
this test is similar'to a methodie‘mployed. by the
General Motors Corporation for determining the
After 1 hour standing:
-
The above
15 examples show our foam inhibitor to be effective
foaming-tendencies of gearing lubricants, but has
been modi?ed in 'the'direction of greater accuracy‘
and in order to make it possible'to record more
comprehensive test' data. ' These .tests are em
ExAMrLn V
ployed by Gulf QilCor'poration and are referred‘
An aviation and automotive lubricant was in 40 to as "Gulf foam tests.”
In order 'to have‘ a standardjof comparison,‘
hibited with.0.05 per cent by weight of disodium
the oils with or. without the anti-foam_-agent_
dioctyl isobutylene diphosphate, prepared by re
should be subjected to the~same specific tests.
There are several tests in use, but. the, ones we
?nd are to be relied upon to- determine the foam-
acting one mole of isobutylene glycol and two
‘ moles of sodium hydroxide with two moles of
phosphorous pentoxide and two moles of octyl
ing or non-foaming characteristics of oil, and.
which will give- exceptionally accurate indica_-_
alcohol according to the procedure used in Ex
ample III. The addition of the aerofoam sup
pressor to the oils did not appreciably change
the physical properties of the oil, as is shown
tions are as follows’.
‘
- Gunr FOAM Tnsr No.1.
by the following tests: '
An agitating means is provided which is an
adaptation of .an ordinary commercial motor
l ‘ Improved oil -
3°” °“
oontatirgng 0.1051t
p3: disodium di
roen
driven household mixer, a "Sunbeam'Mixmaster‘? '
y we g
Model 5, manufactured _by the I Flexible Shaft
octyl isobutylene
Company, Chicago, Illinois. The device employed
diphosphate
in the test is the usual household model with two
Gravity, ° £113 ..................... _.
Visoos ty,
:
as. a
26. a
1, 845
119. 9
535
610
l, 842
118. 9
535
610
slight changesi the turntable of the usual house
hold mixer is replaced by a rigid platform, and a
cylindrical brass‘ ‘container having‘ an‘ inside di
ameter of 7 inches and an inside height of'4
.
°
100 F
0
+5
__
5. 5
5. 5
t ............. _ _
0. 54
0. 44
Neutralization N o ................... __
0. 05
0.05
__
inches is substituted, for the usual household glass .
mixing bowl; The container is ?tted with a gage
for measuring the depth of ‘oil or'oil and foam
therein before and after agitation.
FOAM TEST, GULF N0. 1
65
At end of stirrin :
'
Temperaturg, ° F _______________ -_
80
Volume oilland
i'ozfzm? cc_&_f ..... _.
V0 ume 0 0 an 0am
785
Ratio 0‘ _volume of original oil ' "
Nature oi foam __________________ ..
1' 570
Coarse
Aiierrfl hour standing
em
ure
_______________ _
110111293)!v0<l>ii
andifozlilm, get. ..... -_
ume o 0 an em
78
1
514
‘ 028
Fine
79
78
551
500
1
Rwmmu-
1-1“
-°°°
Nature of foam .................. .-
Coarse
None
' '
'
The agitator device itself QQIImriSes ‘a-pa-ir of _
motor driven beaters which. are of the concave
outside surface type'as described in U. S. Patent
2,161,881, each beater havinga?pair of ‘blades
of the type indicated and ‘being so positioned with
70 respect _to each other that; the two pairs of ‘beater
elements are at right. angles and rotatefin oppqp.
site directions in fclosely- spaced, overlapping
paths. vIn operating position,‘ thepbeatersp are.
perpendicular to the base of the mixer, as shown
75 in U. s. Patent 2,161,881. In-the present test‘,
a,411,e11
11
they are centered in the container. and the bot
tom of the heaters is spaced approximately ‘1|
inch from the bottom of the pan when the latter
is positioned on the rigid platform. with 600 cc.
(:5 cc.) of oil in the container which is level,
the heaters are submerged in the initial oil sample
sothat the bottoms ofthebeaters are?‘ ofone
inch from the bottom of the pan.
"12
tion. These new properties render the com
pounded oil particularly useful for various pur-.
poses; although the decreased tendency of the
' compounded oils to foam has been emphasised
throughout the speci?cation, it is to be under
stood that our invention is not limited to this
feature, and that di?erent compounds of the gen
eral type herein described vary in their-degree of
'
effectiveness and may impart one or more other
The measured sample of 500 cc. (: 5 cc.) of
desirable‘ properties to the lubricating composi
oil is brought to a temperature of '7'!‘ I". (:i: l‘ 1'.)
tion. For example, the compounds described
and the container is then/‘placed in operating
hereinabove inhibit the corrosion of alloy bear
position with the beater elements lowered into
operating position. The motor is started and ad
ings and at the same time reduce the amount of
wear produced as compared with a straight un
justed to a speed of 550 R. P. M. controlled with
in z 10 R. P. M. The heaters agitate the oil and 15 compounded mineral oil. Moreover, the com
beat air into the sample. Agitation is continued
pounds described hereinabove have mild deter
gent properties which are advantageous for cer
for exactly 15 minutes.
tain types of lubrication. In general. the com
The motor is now stopped. The foam level is
pounded oils disclosed in our invention have
determined. and- the temperature of the sample
is measured, the heaters are removed from the 20 better anti-foam, anti-oxidant, oiliness, pressure
carrying. and anti-ring sticking properties than
oil, and any oil or foam adhering to the heaters
the same type of uncompounded oils.
is permitted to drain into the container. which
It will be apparent to those skilled in the art
takes one or two minutes. It is then possible
that our invention is not limited to the details
to calculate the ratio of the volume of oil and
foam to the volumes of the original oil, ,with 25 or examples given hereinabove for clearness and
understanding only, and no unnecessary limita
correction for any temperature changes. The
tions should be understood therefrom, but may
container is removed and allowed to stand free
variously be practiced and embodied within the
from drafts for one hour, measured from the
scope of the appended claims.
time the stirring is stopped. The volume and
temperature measurements are taken again, and 80 What we claim is:
1. A mineral oil composition resistant to foam- '
serve to indicate stability or permanence of the
ing comprising a major amount of a mineral oil
foam produced.
»
and an amount at least su?icient to reduce the
The test procedure may, of course, be varied,
foaming tendency of said oil of a salt of an alkyl
as for example, by changing the volume of the
sample, the speed of agitation or the time of 35 alkylene diphosphate having ‘the following for
agitation, or by taking the ?nal measurements
mula:
.
at an earlier or later period. The inhibited 'oil
may be agitated at higher temperatures than"
77° F., depending on the service conditions to
which the oil may be applied. It is sometimes 40
found that some oils will foam at higher tem
peratures even with the aerofoam inhibitor, while
wherein R. represents an alkyl group containing 1
they will not foam at lower temperatures. Such
is usually the case with the dispersed type of oil
to 18 carbon atoms, Y is a suhstituent of the
aerofoam inhibitor. However, in the test re 45 class consisting of monovalent metals and aihl
groups, x represents a constituent of the class
ferred to in the speci?c example above, the pro
cedure was precisely as indicated.
_
consisting of metals and an organic ammonium
group derived from the class consisting of hetero
GUl-I‘POAITISTNO.2
cyclic nitrogen bases and dialkylaryl amines, m
More violent agitation may be employed if a 50 is a number corresponding to the valence of X.
still more drastic test is required, as is the case
in Gulf foam test No. 2 which uses a higher speed
and n is 2 to 6.
of rotation, namely 900 R. P. M., but is similar in
the other respects to Gulf foam test No. 1.. In
portion of said salt of an alkyl alkylene diphos
phate is between 0.01 and 1.0 per cent by weight
2. The composition of claim 1 wherein the pro
some very low viscosity oils considerable foam 55 of the composition.
may develop during agitation, which disappears
very quickly when agitation is stopped. These
3. The mineral oil composition of claim 1
wherein said salt of an alkyl alkylene diphosphate
is potassium tri-octyl ethylene diphosphate.
conditions are found, for example, in marine
turbine lubricating systems (which use light oils)
4. A mineral oilcomposition resistant to foam
at the point where the returned oil is discharged 00 ing comprising a major amount of mineral oil
rapidly into a reservoir.
and an amount at least suillcient to reduce the
foaming tendency of said oil of a mixed salt
GULI‘ Fons T!!!‘ No. 3
In Gulf foam test No. 3 a brass air distribut
ing mat, containing a No. 40 ?lter paper, dis
tributes 10 liters of air per hour uniformly
of an alkyl alkylene diphosphate having the fol
o5 lowing formula:
through about 230 cc. of oil in a one liter grad
uate. Air is bubbled through the 230 cc. of oil
maintained at 77" C. for a period of 10 minutes.
The nature and the amount of foam are ob 70
served and recorded.
The present invention covers the incorporation
of glycol esters of substituted acid of phosphorus
in a mineral oil, imparting new, unpredictable,
and highly desirable properties to the composi
‘
2,41 1,671
13
14
wherein CnHzn represents an alkylene group, n
6. The mineral oil composition of claim 4
wherein the mixed salt of an alkyl alkylene di
is from 2 to 6, Y represents a monovalent metal,
phosphate is potassium dimethylaniline di-octyl
R represents alkyl groups containing 1 to 18 car
ethylene diphosphate.
bon atoms, and X represents an organic amine
selected from the class consisting of dialkylan in
7. The mineral oil composition of claim 1
wherein said salt of alkyl alkylene diphosphate
ilines and heterocyclic nitrogen bases. '
5. The composition of claim 4 wherein the pro
is disodium di-octyl isobutylene/diphosphate.
portion of the mixed salt of an alkyl alkylene di
phosphate is between 0.01 and 1.0 per cent by
10
weight of the composition.
HERSCHEL G. SMITH.
TROY L. CANTRELL.
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